Spray cooled product and process



Patented May 12, 1953 assenza e@onsmarroni;eraanrimesse4 .IohnrR'osa Ramsey, N. J., assgnqlttn; C

Palmolivegreet.. Compensi. Jersey Citar-,z ,elawara Serie! This invention rel,ai-.esito`v` iifnprov-ements in the spray processing. of normally solid lesters of fatty acidsand aliphatic polyhydroiry compounds, and more particularly the solidt partial esters 0f-L fatty acids and pol-yhydric alololiols.-A

In the manuiacture of emulsions, creams, and various pharmaceutical and cosmetie preparations and the lilge, comrnercial-use h-.asbeenmade ofithesolid partial esters of fattyacidsand polyhydricV alcolmls,` i. e. the glycol and-gylceryl fatty acidj esters, particularlythe monor andfd-i-stearates. These normally, Wax-like solid esters are preferably converted-`into a conVenientpa-rtiele form so that they may; barriere easily transported ....ctureqf. $11911. prediseenerallr ifeciedjhr heating.. the :Que pro sa il it is. immedandf Whilel Stili in liquid tendu sprar inta. sufcientlr c0011 aime .here 11.0. Cause soli'dfcation of the spray droplets of the melted ester in the form orsolidparticles. The resulting Spray-@Qled product cemnrises., nertlesof relatively uniform siza. which. p rt' le may be nirelled, by raryins thenoszle pressure and conditions. under which the..v particles. are. caused to solidiiy. For a more detailed descriptioni4 M,a process for spray-.cooling such solid fatty acid partial esters, reference may be made to the copending patentlappl-icationy of `Harolcl- Dwaine Allen, and Clarence., Joseph Arrowsmith, Ser; No. 24S-,4.38, filed May 2l, 1947...

These commercialfatty-v acidv ester products usually contain impurities, such asv unsaturated free fattyy acids, which.,.areV read-ily oxidized; or function in some mannentoeatalyze a chemical reaction with any oxygen present to produce colorloodies, Opry-:productcarbonylcompounds, which. ten-d to producea product havmganundesirable-colorer odor, er Suchdeleterious efiects. are` accelerated dur-ing` spray cooling of they produc-t due vto the exposureofthelv finely dhzidedfparticles. of the. melted ester to oxidation at relatively high temperatures and underfcondiitions conducive to oxidation lor related chemical reeetienswhiehis undesirable...

Me ods. of renewing. unseturatee impurity i@ iai-112 12J-@dect Q r .uct-which e Qf semola-a... sans It hasnowf beenv discovered; that:V an improved sprayeceoled ester produc-t: canbe produced from commercial,gradesiofthese partial'esters otifatby acids, and@ polyhycrriaalcohol-s Withoutf removing suela unsaturated portionsfor izr-ipuritiesVr 'Eheim-.- prevede results4 are: obtained by.- incorporatingr a ema-1t amount; of arr antioxidant or.f stabilizing agent. The; addi-tienagent'. functions both aslv an antioxidant, inhibiting oxidation ot the. ester dur-f ing spray cooling, and; asav stabilizing',- anlf plie.- seiw'fingv agent:` to provideI a.A product. hayillg goed color` andz'olremical stability; The stabilizingfagent may be addedduringthepreparati-on ofthe fatty acid partial estense that litfbeeomes a, constituent partfthereer; orthefsanremay beincorporatedn the molten ester prior to spray-coating@ prOduGe L /products, in the form ofd-iscifete .particles elrpelletscontainina the preservingagent.4 Thusf: in are comienceY with the present invention,` a., spraycooledI product: composed; et; fatty acid' partiell estersof-rpolyhydrie alcohols isgpreparecifwhchi Lis markedly' sunerion in color andchemical .Stability in; comparison with a; like produca not. spray cooledi in thepresence .ot such apreservin-g: agent.

It; is; an izfnportant` feature of i the present; in.- rention .to;naironlyipreventy oxidaten'off Athe/ester hutY the;` formation of color bodies.A during the Sprasfecoolina: operation. ori during; subsequent storage anat-use. Byvincoryporatirrgan eifective amount: of an antioxidant; which; does not Off itself` causa diesel ratieni and: carrying out; the inacperatiensitispo ble Seres-aaai Storage@ use.;` uni-.term ..1tfrieolifar,A asaltan -berstored .in c; or similar reeeptacleswithout AfearGasser se;

lasciar-assuma no oneheretofrer pm.-

even y and;

. antioxidant prop,- iiaateasenerinthses@ malty solidypartialfesters offiattyaeids and polylalydric-alcoholsprior-to. spray'. cooling@ In.- t;h l5

manner the fatty acid ester is not only protected from the oxidative effects otherwise produced during the heating and spray cooling operations, but in addition, the process results in the production of a finished spray cooled product which is lighter in color and more stable.

As stabilizing agents which may be used, the phenolic and hydroxy aromatic derivative compounds are effective. Tin oxide and its salts may also be used for this purpose. Examples of phenolic type compounds which may be used are isopropyl ortho cresol, n-propyl ortho cresol, monobutyl meta cresol, 4-6 ditertiary butyl-meta cresol, 2-6 ditertiary butyl para cresol, diamyl phenol, 5 methyl-2 isopropyl phenol, l-hydroxy-2 methoxy-benzene, and the like compounds. Where a relatively non-toxic stabilizer is desired, as in the preparation of edible fatty esters, hydroxy benzene derivative compounds such as nordihydroguaiaretic acid may be utilized. The compounds may be used alone or in combination. Further, to enhance the stabilizing properties of the hydroxy aromatic compounds the addition of a trace of other substances having a synergistic effect may be made. For example, to the stabilizing agent there may be added 0.002% by weight citric or ascorbic acid, or a trace of phosphoric acid to produce this desired effect. The amount of stabilizer incorporated in the ester will depend upon the ester and the relative effectiveness of the stabilizing agent which it is desired to employ. In general, the amount used ranges from about 0.01 to 5% by weight of the ester. Preferably less than 1% is employed and ordinarily 0.2 to 0.5% is suflicient.

The preferred manner of carrying out the process, comprises thoroughly admixing the stabilizer with the fatty ester to be spray cooled, using an inert carrier if desired i. e. light mineral oil, after which the mixture is heated to form a melt. The fatty ester containing the stabilizing material and heated to a molten state is then sprayed as fine particles or droplets in a current of moving gas, generally air, to cool and solidify the ester in the form of discrete particles. Contact of the sprayed material with the moving gas rapidly cools the liquid particles of the ester producing a finished product in the form of discrete particles wherein the stabilizer is thoroughly and uniformly distributed throughout the same. A spray cooled ester product is thus produced which is of uniformly good color, and which does not darken or develop rancid odors when stored over long periods of time.

Although it is preferred to incorporate the stabilizer prior to spray-cooling to form the pellets of the fatty acid ester, the stabilizer may be incorporated concurrently during spray-cooling, as for example by uniformly dispersing therein a concentrate comprising a melt or a liquid mixture of said ester carrying the stabilizer so that the required amount of stabilizer is added to the melt to protect it against the oxidative effects to which it is subjected during spraying and cooling. A nnished spray cooled product is thus produced which contains the required amount of stabilizing agent to prevent such detrimental oxidative effects from taking place during spraying as well as during subsequent storage and use.

The invention is particularly useful in stabiliz-A ing normally solid commercial fatty esters, such as mono and polyhydroxy fatty esters, during spray-cooling to form the same into small discrete particles, although the invention is not to be understood as limited specifically thereto. Examples of partial esters of fatty acids and polyhydric alcohols which may be spray cooled to form a stabilized product which is in the form of discrete particles, or pellets, are mono esters of glycol i. e. ethylene glycol monostearate, diethylene glycol monostearate, propylene glycol monostearate, ethylene glycol mono myristate, ethylene glycol mono laurate, diethylene glycol mono myristate, propylene glycol mono myristate; the diesters, i. e. ethylene glycol di-stearate; also glycerol esters i. e. glycerol monostearate, glycerol mono myristate, tallow monoglyceride and the like as Well as the esters of unsaturated fatty acids such as oleic, linoleic, etc. and polyhydric alcohols. Mixtures of different fatty acid esters may also be utilized in making spray cooled products in accordance with the present invention.

The following examples illustrate how the invention may be utilized.

L'aample I Example II To a quantity of ethylene glycol mcnostearate of commercial grade there is incorporated 0.3% by weight of n-propyl ortho cresol and the mixture is heated to form a molten mass which is sprayed to form pellets similarly as in Example I.

Example III u To a quantity of glycerol monostearate of commercial grade there is added 0.3% by weight of di-butyl meta cresol, and the fatty acid ester spray-cooled to form pellets similarly as in Exn ample It Example IV To fty pounds of ethylene glycol mono myristate containing small amounts of impurities there is incorporated one-quarter of a pound of monobutyl meta cresol, and the mixture melted and spray cooled to form a product having discrete particles containing the cresol preservative.

Example V To a quantity of ethylene glycol mono laurate of commercial grade, and which is to be spray cooled as in Example I, there is incorporated 0.2% by weight of isopropyl ortho cresol. The melted mixture is then subjected to spray cooling to form a pellet like mass having improved color :and stability.

Example VI To a quantity of diethylene glycol mono stearate containing small amounts of impurities there yis added 0.5% by weight of 2-6 ditertiary butyl para cresol containing 0.002% by weight citric acid. The mixture is heated to a melting temperature and spray cooled to provide a finished product made up of discrete particles.

Example VII To a quantity of rened bleached tallow monoglyceride there is incorporated 0.01% by weight of nordihydroguaiaretic acid containing 0.003%

by weight of phosphoric acid, and the mixture heated to form a melt which is spray cooled as described in Example I. A pellet-like monoglycerol ester product of improved color and stability is produced which is edible, and which may be used in the preparation of various types of foodstuiis.

Eample VIII To a quantity of diethylene glycol mono stearate of commercial grade there is added 0.1% by Weight tin stearate. The ingredients, after being thoroughly admixed, is heated to form a molten mass which is then subjected to spray cooling to form the ester into discrete particles as described in Example I.

Example IX To a quantity of rened tallow monoglyceride there is incorporated 0.2% by weight tin oxide, the powder-like oxide being thoroughly admmed into the tallow While the same is heated to form a melt. The melted ester is then subjected to spray cooling to produce a finished product comprising discrete particles.

Although the invention has been vdescribed in detail, with specic examples given, such examples 4are understood to be merely illustrative and are not limitative thereof inasmuch las modifications and substitutions may be made within the spirit and scope of this invention, as will be apparent to those skilled in the art. Accordingly, the invention is limited as indicated in the appended claims.

What is claimed is:

1. A spray-cooled organic composition comprising solid pellets made up essentially of a normally solid partial ester of a fatty acid and an aliphatic polyhydroxy alcohol and containing a minor proportionate amount of a stabilizer consisting of an hydroxy aromatic yderivative compound having a single benzene nucleus and an alkyl radical having up to 5 carbon atoms, said stabilizer amounting to 0.01 to 5% by Weight of the spray cooled ester product and bein-g uniformly distributed throughout each pellet.

2. The process which comprises heating normally solid partial esters of fatty acids :and aliphatic polyhydroxy compounds to form a molten mass, admixing therewith a small percentage amount of a stabilizer having antioxidant properties consisting of an hydroxy aromatic derivative compound to stabilize the esters against oxidation and discoloration, said compound having a single benzene nucleus and an alkyl radical having up to 5 carbon atoms, and spraying the resulting mixture in ne droplet form into a cooled gaseous medium to solidify the same into solid discrete particles.

3. The process as set forth in claim 2 in which diamyl phenol is utilized as the stabilizer.

4. The process as set forth in claim 2 in which propyl cresol is utilized as the stabilizer.

5. The process as set forth in claim 2 in which butyl cresol is utilized as the stabilizer.

JOHN ROSS.

References Cited in the i'lle of this patent UNITED STATES PATENTS Number Name Date 1,329,845 Overbeek Feb. 3, 1920 2,107,069 Evans Feb. 1, 1938 2,377,610 Brown June 5, 1945 2,407,616 Phelps Sept. 10, 1946. 2,423,449 Heald et al. July 8, 1947 2,451,748 Kraybill Oct. 19, 1948 2,457,741 Shipner Dec. 28, 1948 2,511,803 Hall June 13, 19,50 

1. A SPRAY-COOLED ORGANIC COMPOSITION COMPRISING SOLID PELLETS MADE UP ESSENTIALLY OF A NORMALLY SOLID PARTIAL ESTER OF A FATTY ACID AND AN ALIPHATIC POLYHYDROXY ALCOHOL AND CONTAINING A MINOR PROPORTIONATE AMOUNT OF A STABILIZER CONSISTING OF AN HYDROXY AROMATIC DERIVATIVE COMPOUND HAVING A SINGLE BENZENE NUCLEUS AND AN ALKYL RADICAL HAVING UP TO 5 CARBON ATOMS, SAID STABILIZER AMOUNTING TO 0.01 TO 5% BY WEIGHT OF THE SPRAY COOLED ESTER PRODUCT AND BEING UNIFORMLY DISTRIBUTED THROUGHOUT EACH PELLET. 